PVDF pyrolyzate adsorbent and gas storage and dispensing system utilizing same

ABSTRACT

A polyvinylidene fluoride (PVDF) pyrolyzate adsorbent is described, having utility for storing gases in an adsorbed state, and from which adsorbed gas may be desorbed to supply same for use. The PVDF pyrolyzate adsorbent can be of monolithic unitary form, or in a bead, powder, film, particulate or other finely divided form. The adsorbent is particularly suited for storage and supply of fluorine-containing gases, such as fluorine gas, nitrogen trifluoride, carbo-fluoride gases, and the like. The adsorbent may be utilized in a gas storage and dispensing system, in which the adsorbent is contained in a supply vessel, from which sorbate gas can be selectively dispensed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation under 35 USC 120 of U.S. patent application Ser. No. 13/329,254 filed Dec. 17, 2011 in the names of Shaun M. Wilson and Edward A. Sturm for “PVDF PYROLYZATE ADSORBENT AND GAS STORAGE AND DISPENSING SYSTEM UTILIZING SAME”, issued Mar. 25, 2014 as U.S. Pat. No. 8,679,231, which claims the benefit under 35 USC 119 of U.S. Provisional Patent Application No. 61/434,219 filed Jan. 19, 2011 in the names of Shaun M. Wilson and Edward A. Sturm for “PVDF PYROLYZATE ADSORBENT AND GAS STORAGE AND DISPENSING SYSTEM UTILIZING SAME.” The disclosures of U.S. patent application Ser. No. 13/329,254 and U.S. Provisional Patent Application No. 61/434,219 are hereby incorporated herein by reference, in their entireties, for all purposes.

FIELD

The present disclosure relates to an adsorbent useful in sorbent-based gas storage and dispensing systems, e.g., for fluorocompound gases such as gaseous fluorides, and to methods of making and using such adsorbent and gas storage and dispensing systems.

DESCRIPTION OF THE RELATED ART

The use of molecular fluorine in industry has been limited due to its toxic nature and high degree of reactivity. There are nonetheless a number of applications in which the use of molecular fluorine is necessary, such as the synthesis of uranium hexafluoride and sulfur hexafluoride, and cleaning of semiconductor processing tools (CVD reactors, ion implanters, epitaxial chambers, etc.). Fluorocompound gases such as NF₃ can also be used in cleaning of semiconductor processing tools.

In the supply of industrial gases, a wide variety of gas source packages are utilized. In semiconductor manufacturing and other industrial processes, adsorbent-based gas storage and dispensing systems have been developed, which provide safe and effective supply sources for numerous process gases. One such adsorbent-based gas storage and dispensing system is commercially available from ATMI, Inc. (Danbury, Conn., USA) under the trademark SDS. By utilizing physical adsorbent materials for storing gases in an adsorbed state, and dispensing same from the adsorbent under desorption conditions, gases can be stored at low pressures for enhanced safety, relative to high-pressure gas cylinders that have been conventionally employed in the past.

One adsorbent material that has been usefully employed in such sorbent-based gas storage and dispensing systems is a carbon adsorbent that is formed by pyrolysis from polyvinylidene chloride (PVDC). Such adsorbent is highly effective for gases such as arsine, phosphine, silane, boron trichloride, boron trifluoride, germanium tetrafluoride, hydrogen selenide, hydrogen telluride, and a wide variety of other acid gases, organometallic gaseous reagents, etc., but our experience suggests a potential exists for gases such as fluorine and NF₃ to decompose on such carbon adsorbent during storage.

Further, despite the many desirable characteristics and advantages attendant the use of physical adsorbent media for storage and dispensing of gases, currently there is no adsorbent commercially available that has demonstrated utility to safely and reversibly store molecular fluorine or NF₃.

SUMMARY

The present disclosure relates to an adsorbent useful in sorbent-based gas storage and dispensing systems, and to methods of making and using such adsorbent and gas storage and dispensing systems.

The disclosure in one aspect relates to polyvinylidene fluoride (PVDF) pyrolyzate carbon adsorbent.

The disclosure in another aspect relates to a carbon adsorbent of such type, having gas adsorbed thereon.

In another aspect, the disclosure relates to a carbon adsorbent of the foregoing type, disposed in a fluid storage and dispensing vessel configured to store gas having sorptive affinity for the carbon adsorbent in an adsorbed state, and to discharge gas desorbed from the carbon adsorbent under dispensing conditions.

A further aspect of the disclosure relates to a method of gas handling, comprising one of (i) adsorbing on, and (ii) desorbing gas from, a polyvinylidene fluoride (PVDF) pyrolyzate carbon adsorbent.

Other aspects, features and embodiments of the disclosure will be more fully apparent from the ensuing description and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic flowsheet for a process for forming a PVDF pyrolyzate adsorbent in accordance with one embodiment of the present disclosure.

FIG. 2 is a schematic representation of a gas storage and delivery system utilizing a PVDF pyrolyzate adsorbent, according to one embodiment of the disclosure.

DETAILED DESCRIPTION

The present disclosure relates to an adsorbent useful in sorbent-based gas storage and dispensing systems, and to methods of making and using such adsorbent and gas storage and dispensing systems.

The disclosure in one aspect relates to a polyvinylidene fluoride (PVDF) pyrolyzate carbon adsorbent. Carbon adsorbent of such type can be readily formed by pyrolysis of a polyvinylidene fluoride (PVDF) polymer as hereinafter more fully described. Such carbon adsorbent may be of monolithic form, or alternatively may be of particulate form, e.g., as beads, powders, or the like, or of other forms. The carbon adsorbent may be formed by a pyrolysis process wherein the pyrolysis of the PVDF polymer has been carried out to convert the polymer into a high capacity microporous active carbon having low reactivity to fluorine-containing gases. This can entail a pyrolysis carried out at suitable temperature, e.g., temperature of 400-600° C. or higher.

The carbon adsorbent of the present disclosure is usefully employed as an adsorbent material for a wide variety of gases. The carbon adsorbent can have a gas adsorbed thereon such as a fluorine-containing gas, e.g., fluorine gas, boron trifluoride, nitrogen trifluoride, carbofluorides, etc. The carbon adsorbent, while having utility for adsorptive storage and dispensing of fluorine or other fluorocompound gases, can be usefully employed with any gases having sorptive affinity for the carbon adsorbent. Examples of gases that may be utilized as sorbate gas species adsorbed on and desorbable from the carbon adsorbent of the disclosure, include, without limitation, arsine, phosphine, boron trichloride, boron trifluoride, silane, germane, phosgene, diborane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, deuterated hydrides, halide (chlorine, bromine, fluorine, and iodine) compounds, organometallic compounds, nitrogen trifluoride, fluorine, hydrogen fluoride, diboron tetrafluoride, and carbofluoride compounds.

In another aspect, the disclosure relates to a carbon adsorbent of a type as variously described herein, disposed in a fluid storage and dispensing vessel configured to store gas having sorptive affinity for the carbon adsorbent in an adsorbed state, and to discharge gas desorbed from the carbon adsorbent under dispensing conditions, as a gas storage and delivery apparatus comprising the carbon adsorbent of the present disclosure.

In such gas storage and delivery apparatus, a gas may be adsorbed on the carbon adsorbent, such as a fluorine-containing gas, e.g., selected from among fluorine, nitrogen trifluoride, or other highly reactive fluorine containing gas, or other gas as hereinabove described. The gas storage and delivery apparatus may comprise a storage vessel for retaining the carbon adsorbent and gas adsorbed thereon. The carbon adsorbent in such a gas storage and delivery apparatus can be of a monolithic form, or of bead, powder, film, particulate, or other suitable form, as indicated above. In various embodiments, the carbon adsorbent comprises a fluorine-containing group/complex formed by pyrolysis of the PVDF polymer to reduce reactivity of the carbon adsorbent to fluorine-containing gases. Monolithic forms of the carbon adsorbent may be of any suitable size and dimensions, and may for example be in the form of pucks or discs that are vertically stackable on one another in a vessel to form a stacked array in which the successive pucks or discs are in face-to-face abutting relationship to one another. The monolithic form may include rods or cylinders of the carbon adsorbent, or rectangular parallelepiped geometric forms.

The disclosure in a further aspect relates to a method of gas handling, comprising one of (i) adsorbing on, and (ii) desorbing gas from, a polyvinylidene fluoride (PVDF) pyrolyzate carbon adsorbent of the disclosure. Such method may comprise desorbing gas from the carbon adsorbent, and utilizing the desorbed gas in the manufacture of a semiconductor, flat panel display, or solar product. Semiconductor products may include integrated circuitry devices and device structures, microelectromechanical devices, optoelectronic devices, etc. Flat-panel displays may include computer monitor and television display products. Solar products may include photovoltaic cells and thermal solar arrays.

The disclosure also contemplates a method of storing and delivering gas, comprising adsorbing a gas on, and desorbing gas from, a carbon adsorbent of the present disclosure. The carbon adsorbent may be disposed in a storage vessel including a valve head assembly that is coupleable with associated flow circuitry. The carbon adsorbent may be formed in such manner as to reduce reactivity of the carbon adsorbent to fluorine-containing gases, relative to a corresponding carbon adsorbent not derived from PVDF polymer.

The present disclosure is based on our discovery that by using polyvinylidene fluoride (PVDF) as a starting material, a pyrolyzate adsorbent can be formed that is suitable for use as an effective gas storage medium for a wide variety of gases, including fluorine-containing gases such as fluorine and nitrogen trifluoride, as well as non-fluorine-containing gases. The processing of the PVDF starting material may be carried out to produce PVDF pyrolyzate adsorbent material of desired porosity, pore structure and pore size distribution, within the skill of the art, based on the disclosure herein.

FIG. 1 is a schematic flowsheet for a process for forming a PVDF pyrolyzate adsorbent in accordance with one embodiment of the present disclosure.

As illustrated in such flowsheet, a shaped body is formed of polyvinylidene fluoride. The shaped body may be of any suitable size, and may be geometrically regular or irregular in character. The shaped body may be shaped so that after processing including pyrolysis the pyrolyzate mass closely conforms to the interior volume of a gas storage and dispensing vessel. For example, the gas storage and dispensing vessel may be of a cylindrical geometry, closed at one end and open at the other, and the pyrolyzate mass may be of corresponding cylindrical form as a result of use of a mold or other form to provide such geometry. In such manner, the pyrolyzate mass may be introduced to the open end of the gas storage and dispensing vessel, during the fabrication thereof, with the vessel being closed by a top plate or valve head structure to provide an enclosed interior volume containing the PVDF pyrolyzate adsorbent.

As an alternative, the polyvinylidene fluoride starting material may be provided in resin form in the first instance, to fill a predetermined amount of the interior volume of the gas storage and dispensing vessel, so that subsequent processing including pyrolysis is carried out in situ in the vessel. In still other embodiments, the starting material can be a PVDF polymer powder that is processed without an initial shaping process, to produce a corresponding PVDF pyrolyzate of powder form.

The PVDF starting material may be a homopolymer of vinylidene fluoride or alternatively a copolymer comprising PVDF and one or more other polymer components, e.g., as a polymerization product of comonomers including vinylidene fluoride and one or more other comonomer species. The PVDF starting material may also comprise other materials such as plasticizers, surfactants, or other additives, adjuvants, etc., as necessary or desirable in a given application to provide a PVDF precursor with certain processability or a pyrolyzate adsorbent of desired character.

Subsequent to forming a shaped body of PVDF starting material, as illustrated in the flowsheet of FIG. 1, the PVDF body is baked out at elevated temperature to degas the material. Such bake-out may be carried out at any suitable temperature, e.g., temperature in a range of from 90° C. to 120° C., as appropriate to carry out pre-pyrolysis processing of the PVDF material. In other embodiments, such pre-pyrolysis processing is not carried out, and the starting material is of suitable character for pyrolysis without bake-out or degassing of the starting material.

The pyrolysis of the PVDF body is carried out by heating to a suitable elevated temperature, e.g., temperature in a range of from 800° C. to 2000° C. at a controlled ramp rate, to form the PVDF pyrolyzate adsorbent of desired porosity character. The pyrolysis operation may be carried out to produce a PVDF pyrolyzate that is highly porous in character, with desired porosity, loading capacity, bulk density and other characteristics. It will be recognized that the time-temperature relationship of the pyrolysis operation can be substantially varied, together with pyrolysis conditions such as pressure, ambient environment, etc., to achieve such desired characteristics. Accordingly, the pyrolysis operation conditions may be initially determined using sample PVDF bodies, with variation of the pyrolysis conditions as necessary to empirically establish and define a process envelope of pyrolysis conditions for the subsequent production of the PVDF pyrolyzate adsorbent.

The PVDF pyrolyzate may include, in various specific embodiments, porosity including pores of a size in a range of from 0.2 to 5 nanometers, e.g., with at least 30% of overall porosity of the adsorbent comprising pores having a size in a range of from about 0.3 to about 0.72 nanometer, and at least 50% of the overall porosity comprising pores of diameter <2 nanometers.

The PVDF pyrolyzate carbon material in various embodiments may be formed by pyrolysis and optional activation at temperatures in a range of from 400° C. to 1400° C. The PVDF pyrolyzate adsorbent in various embodiments has a bulk density of at least 0.6 grams per cubic centimeter, e.g., a bulk density of from about 0.6 to about 1.8 grams per cubic centimeter.

The PVDF starting material in other embodiments is pyrolyzed at temperature in a range from 400° C. to 900° C., in the absence of air, typically under inert atmosphere comprising gas such as argon or nitrogen. At specific stages in the pyrolysis, the PVDF based carbon material may optionally be exposed to an oxidizing atmosphere, e.g., comprising carbon monoxide, oxygen and/or steam, at temperature above 250° C., such as temperature in a range of from 600 to 1300° C.

In some embodiments of the present disclosure, the pyrolysis of the PVDF material can be carried out under “incomplete pyrolysis” conditions, e.g., at temperature in a range of from 400° C. to 600° C., such that a residual amount of fluorine remains within the adsorbent material to provide a particularly low reactivity environment for storage of F₂.

The pyrolysis in other embodiments may be carried out to optimize the sorptive affinity and loading capacity of the PVDF pyrolyzate adsorbent for other fluorine-containing gases, such as nitrogen trifluoride, carbo-fluorides of varying formula (e.g., C_(x)F_(y), wherein x and y are any suitable stoichiometrically appropriate numerical values), etc.

While the PVDF pyrolyzate adsorbent of the present disclosure is described herein with particular application to fluorine-containing gases as sorbate species useful for storage on and dispensing from the PVDF pyrolyzate adsorbent, it will be recognized that the utility of the PVDF pyrolyzate adsorbent is not thus limited, but rather extends to and includes gases of widely varied other types, including other halide gases, hydride gases, organometallic gaseous reagents, silanes, etc.

In general application, the form of the PVDF carbon pyrolyzate will depend on the shape or form of the PVDF resin precursor material and its shape or conformation. The PVDF carbon pyrolyzate may be formed from discrete resin particles of appropriate size, to yield activated carbon particles, granules, beads, films or the like. The precursor material, as mentioned, may be pyrolyzed in a vessel or form structure imparting a unitary character to the pyrolyzate material, e.g., so that it is formed as a monolithic pyrolyzate.

The monolithic pyrolyzate may have any suitable size and shape characteristics appropriate to its desired end use. For example, the monolithic pyrolyzate may be in the form of a cylinder, block, brick, or other geometrically regular or irregular shape of desired size and character.

The pyrolysis process may be carried out to produce a PVDF pyrolyzate adsorbent having fluorine permeability that may for example be at least 100 cc/psi/cm²/min at 275 kPa, and preferably at least 200 cc/psi/cm₂/min, and can for example in specific embodiments be in a range from 100 to 600 cc/psi/cm²/min or even higher. Illustrative embodiments of the PVDF pyrolyzate may have at least 100, at least 200, at least 300 or at least 500 cc/psi/cm²/min permeability for fluorine gas.

The particle size of the starting PVDF material in some embodiments may for example be primarily in a particle size range of from 100 to 250 microns, with a major fraction (>½) of particles being in the range of 150-200 microns. In other embodiments, the particle size distribution may vary and a major fraction of the PVDF particles may in a range of 100-150 microns. Such particulate starting material may be used to produce bead, film, or particulate form PVDF pyrolyzate adsorbent.

The particulate starting PVDF material may be pyrolyzed in various embodiments, so that the particles are consolidated by compaction and applied pressure to form a monolithic pyrolyzate material, and small amounts of plasticizer can be added to the precursor PVDF material, e.g., from 0.2 to 2% by weight in various embodiments, however such plasticizer material can be added in greater or lesser amounts in other specific embodiments of the disclosure. Such weight percentages of plasticizer are based on the total weight of the PVDF starting material.

It will be recognized from the foregoing that the pyrolysis operation may be carried out using PVDF starting material of widely varied character, to produce PVDF pyrolyzate adsorbent of correspondingly varied character.

FIG. 2 is a schematic representation of a gas storage and delivery system utilizing a PVDF pyrolyzate adsorbent, according to one embodiment of the disclosure.

As shown, the storage and dispensing system 200 comprises a storage and dispensing vessel 204 that is joined at its upper portion to a valve head 206 comprising part of a dispensing assembly including manual actuator 208 for the valve head on the cylinder. In lieu of such manual actuator, an automatic valve actuator could be employed, such as a pneumatic valve actuator or actuator of other suitable type.

The vessel 204 can be formed of any suitable material of construction having stability in contact with the gas(es) intended to be stored therein, e.g., comprising material such as metals, glasses, ceramics, vitreous materials, polymers, and composite materials. Illustrative metals for such purpose include steel, stainless steel, aluminum, copper, brass, bronze, and alloys thereof. As an example, high nickel content alloys are useful materials of construction for vessels used for storage of fluorine. The valve head is joined by means of coupling 210 to a dispensing conduit 212 having disposed therein a pressure transducer 214, an inert purge unit 216 for purging the dispensing assembly with inert gas, a mass flow controller 220 for maintaining constant flow rate through the dispensing conduit 212 during the dispensing operation, and a filter 222 for removing particulates from the dispensed gas prior to its discharge from the dispensing assembly.

The dispensing assembly further comprises a coupling 224, for matably engaging the dispensing assembly with downstream piping, valving, or other structure associated with the locus of use of the desorbed fluid, e.g., involving a semiconductor manufacturing facility such as a chemical vapor deposition chamber. The fluid storage and dispensing vessel 204 is shown partially broken away to show the interior PVDF pyrolyzate adsorbent body 205.

The valve head of the vessel illustratively shown in FIG. 2 may include a fill port for introduction of sorbate gas to the PVDF pyrolyzate adsorbent in the interior volume of the vessel 204. Filling of the vessel may be carried out in any suitable manner, e.g., with monitoring of pressure during the fill operation, and with the introduction of sorbate gas being at sufficiently low flow rate so that the heat of adsorption effects can be dissipated in an efficient manner, to enable the vessel to be loaded with sufficient charge of sorbate gas to achieve high loading capacity of such gas on the adsorbent in the vessel.

The pressure monitoring during the fill operation may be carried out with introduction of gas in successive steps, whereby pressure drops in the vessel due to adsorption of the sorbate gas, following which the introduction of gas is resumed, and such stage-wise filling is carried out until the desired loading is achieved. Upon achievement of the desired loading of the vessel with the sorbate gas, the fill port is closed, and the charged vessel may thereafter be transported to an end use site, for gas dispensing service.

Subsequently, in use of the gas storage and delivery system, the adsorbed sorbate gas is desorbed under dispensing conditions, so that the desorbed gas can be discharged from the vessel through the valve in the valve head assembly, and flowed to a locus of use, such as a gas-utilizing apparatus. In various embodiments, the sorbate gas is fluorine gas, which is utilized for chemical synthesis. In other embodiments, the sorbate gas is fluorine gas or nitrogen trifluoride gas, which is utilized for cleaning of semiconductor process equipment such as vapor deposition chambers, ion implant chambers, etc. The desorption of the sorbate gas in the dispensing operation may be carried out by pressure differential, in which the gas storage and delivery system is coupled with flow circuitry at a lower pressure level than in the vessel, as a result of which the adsorbed gas desorbs from the PVDF pyrolyzate adsorbent, and flows to the flow circuitry.

Alternatively, the desorption of the sorbate gas can be effected by imposition of a concentration gradient, such as by flowing a non-sorbable, e.g., inert, carrier gas through the interior volume of the vessel, so that the resulting concentration gradient effects desorption of the sorbate gas and entrainment thereof in the carrier gas stream subsequently discharged from the gas storage and dispensing vessel.

As a still further desorption modality, the PVDF pyrolyzate adsorbent may be heated in a controlled manner, to effect thermally-mediated desorption of the sorbate gas for subsequent discharge from the gas storage and dispensing vessel.

It will be recognized that the foregoing modes of effecting desorption can be carried out in various combinations with one another, to achieve a desired dispensing flow of the desorbed sorbate gas.

Thus, the present disclosure provides a PVDF pyrolyzate adsorbent that may be usefully employed in a variety of applications requiring adsorption storage and subsequent dispensing desorption of gases. The disclosure also enables the production of PVDF pyrolyzate adsorbent from a PVDF starting material that is readily processed by pyrolysis to yield a pyrolyzate material of the desired character for such gas storage and dispensing applications.

While the disclosure has been set out herein in reference to specific aspects, features and illustrative embodiments thereof, it will be appreciated that the utility of the disclosure is not thus limited, but rather extends to and encompasses numerous other variations, modifications and alternative embodiments, as will suggest themselves to those of ordinary skill in the field of the present disclosure. Correspondingly, the invention as hereinafter claimed is intended to be broadly construed and interpreted, as including all such variations, modifications and alternative embodiments, within its spirit and scope. 

What is claimed is:
 1. A fluid storage and dispensing apparatus, comprising: a fluid storage and dispensing vessel, holding a fluid storage and dispensing medium comprising a polyvinylidene fluoride pyrolyzate carbon adsorbent in a monolithic or particulate form, adapted for fluid to be reversibly adsorbed thereon, wherein the vessel is configured to store adsorbed fluid on the polyvinylidene fluoride pyrolyzate carbon adsorbent, and to discharge fluid desorbed from the polyvinylidene fluoride pyrolyzate carbon adsorbent under dispensing conditions.
 2. The fluid storage and dispensing apparatus of claim 1, further comprising a fluid reversibly adsorbed on the polyvinylidene fluoride pyrolyzate carbon adsorbent.
 3. The fluid storage and dispensing apparatus of claim 2, wherein the fluid comprises one or more of arsine, phosphine, boron trichloride, boron trifluoride, silane, germane, phosgene, diborane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, deuterated hydrides, halide (chlorine, bromine, fluorine, and iodine) compounds, organometallic compounds, nitrogen trifluoride, fluorine, hydrogen fluoride, diboron tetrafluoride, and carbofluoride compounds.
 4. A fluid storage and dispensing apparatus, comprising: a fluid storage and dispensing vessel, holding a fluid storage and dispensing medium comprising a polyvinylidene fluoride pyrolyzate carbon adsorbent adapted for fluid to be reversibly adsorbed thereon, wherein the vessel is configured to store adsorbed fluid on the polyvinylidene fluoride pyrolyzate carbon adsorbent, and to discharge fluid desorbed from the polyvinylidene fluoride pyrolyzate carbon adsorbent under dispensing conditions, further comprising a fluid reversibly adsorbed on the polyvinylidene fluoride pyrolyzate carbon adsorbent, wherein the fluid comprises a fluorine-containing fluid.
 5. The fluid storage and dispensing apparatus of claim 4, wherein the fluorine-containing fluid comprises fluorine gas.
 6. The fluid storage and dispensing apparatus of claim 4, wherein the fluorine-containing fluid comprises NF₃.
 7. The fluid storage and dispensing apparatus of claim 1, wherein the polyvinylidene fluoride pyrolyzate carbon adsorbent is of monolithic form.
 8. The fluid storage and dispensing apparatus of claim 1, wherein the polyvinylidene fluoride pyrolyzate carbon adsorbent is of particulate form.
 9. The fluid storage and dispensing apparatus of claim 1, wherein the polyvinylidene fluoride pyrolyzate carbon adsorbent comprises porosity including pores of a size in a range of from 0.2 to 5 nanometers.
 10. The fluid storage and dispensing apparatus of claim 9, having porosity, wherein at least 30% of the porosity of the polyvinylidene fluoride pyrolyzate carbon adsorbent comprises pores having a size in a range of from about 0.3 to about 0.72 nanometer, and at least 50% of the porosity comprises pores of diameter <2 nanometers.
 11. The fluid storage and dispensing apparatus of claim 1, wherein the polyvinylidene fluoride pyrolyzate carbon adsorbent has a bulk density in a range of from 0.6 to 1.8 grams per cubic centimeter.
 12. The fluid storage and dispensing apparatus of claim 1, wherein the polyvinylidene fluoride pyrolyzate carbon adsorbent has a fluorine gas permeability in a range of from 100 to 600 cc/psi/cm²/min at 275 kPa pressure.
 13. The fluid storage and dispensing apparatus of claim 1, wherein the polyvinylidene fluoride pyrolyzate carbon adsorbent is in the form of discs that are vertically stacked in the fluid storage and dispensing vessel to form a stacked array in which successive discs are in face-to-face abutting relationship to one another.
 14. The fluid storage and dispensing apparatus of claim 13, wherein the polyvinylidene fluoride pyrolyzate carbon adsorbent has a bulk density in a range of from 0.6 to 1.8 grams per cubic centimeter, a fluorine gas permeability in a range of from 100 to 600 cc/psi/cm²/min at 275 kPa pressure, and porosity including pores of a size in a range of from 0.2 to 5 nanometers, wherein at least 30% of the porosity of the polyvinylidene fluoride pyrolyzate carbon adsorbent comprises pores having a size in a range of from about 0.3 to about 0.72 nanometer, and at least 50% of the porosity comprises pores of diameter <2 nanometers.
 15. A method of supplying fluid for use in manufacturing, comprising charging an adsorbable fluid to a fluid storage and dispensing apparatus according to claim 1, for adsorption of the adsorbable fluid on the polyvinylidene fluoride pyrolyzate carbon adsorbent.
 16. The method of claim 15, wherein said charging is carried out in a fill operation wherein pressure of the adsorbable fluid is monitored during the fill operation.
 17. A manufacturing facility comprising a fluid storage and dispensing apparatus according to claim 2, coupled to flow circuitry for delivering fluid discharged from the fluid storage and dispensing vessel under dispensing conditions to a fluid-utilizing apparatus.
 18. A manufacturing facility comprising a fluid storage and dispensing apparatus, comprising: a fluid storage and dispensing vessel, holding a fluid storage and dispensing medium comprising a polyvinylidene fluoride pyrolyzate carbon adsorbent adapted for fluid to be reversibly adsorbed thereon, wherein the vessel is configured to store adsorbed fluid on the polyvinylidene fluoride pyrolyzate carbon adsorbent, and to discharge fluid desorbed from the polyvinylidene fluoride pyrolyzate carbon adsorbent under dispensing conditions, further comprising a fluid reversibly adsorbed on the polyvinylidene fluoride pyrolyzate carbon adsorbent, wherein the fluid storage and dispensing apparatus is coupled to flow circuitry for delivering fluid discharged from the fluid storage and dispensing vessel under dispensing conditions to a fluid-utilizing apparatus, wherein the fluid reversibly adsorbed on the polyvinylidene fluoride pyrolyzate carbon adsorbent comprises fluorine gas or nitrogen fluoride gas, the fluid-utilizing apparatus comprises a semiconductor manufacturing apparatus, and the fluid storage and dispensing apparatus is configured to flow the fluid to the semiconductor manufacturing apparatus for cleaning thereof.
 19. The manufacturing facility of claim 18, wherein the semiconductor manufacturing apparatus comprises a vapor deposition chamber or an ion implant chamber.
 20. A method of manufacturing a semiconductor, flat-panel display, or solar product, comprising supplying gas for said manufacturing from a fluid storage and dispensing apparatus according to claim
 1. 